JP2723763B2 - Electrodes for secondary batteries - Google Patents
Electrodes for secondary batteriesInfo
- Publication number
- JP2723763B2 JP2723763B2 JP4233147A JP23314792A JP2723763B2 JP 2723763 B2 JP2723763 B2 JP 2723763B2 JP 4233147 A JP4233147 A JP 4233147A JP 23314792 A JP23314792 A JP 23314792A JP 2723763 B2 JP2723763 B2 JP 2723763B2
- Authority
- JP
- Japan
- Prior art keywords
- insoluble
- infusible substrate
- powder
- heat
- infusible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000758 substrate Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 229920003026 Acene Polymers 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims 1
- 239000002198 insoluble material Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 238000000748 compression moulding Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は２次電池用電極に係り、
更に詳しくは、芳香族系ポリマーの熱処理物の粉砕物に
ポリテトラフルオロエチレン系結合剤（以下ＰＴＦＥ系
結合剤と記す）を加え、混合・混練し、該混練物を破砕
し、圧縮成型して得られたポリアセン系骨格構造を有す
る２次電池用電極に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode for a secondary battery,
More specifically, a polytetrafluoroethylene-based binder (hereinafter, referred to as a PTFE-based binder) is added to a pulverized heat-treated aromatic polymer, mixed and kneaded, and the kneaded material is crushed and compression-molded. The present invention relates to an electrode for a secondary battery having the obtained polyacene-based skeleton structure.
【０００２】[0002]
【従来の技術】高分子材料は成型性，軽量性および量産
性に優れている。そのため高分子材料のこれらの特性を
生かして、電気的に半導性を有する有機高分子材料がエ
レクトロニクス産業を始めとして多くの産業分野におい
て希求されている。初期の有機半導体はフイルム状ある
いは板状体等に成型することが困難であり、又ｎ型ある
いはｐ型の不純物半導体としての性質を有していなかっ
たため、用途的にも限定されていた。近年、比較的成型
性に優れた有機半導体が得られるようになり、しかもこ
れらの半導体に電子供与性ドーパントあるいは電子受容
性ドーパントをドーピングすることによってｎ型あるい
はｐ型の有機半導体とすることが可能となった。そのよ
うな有機半導体の代表例として、ポリアセチレンがあ
る。ところがポリアセチレンは酸素によって酸化され易
い欠点がある。このため空気中で取り扱うことが困難で
あり、工業材料としては実用性に欠ける。本願の出願人
の出願にかかる、特開昭５９−３８０６号公報には
（Ａ）炭素，水素および酸素から成る芳香族系ポリマー
の熱処理物であって、水素原子／炭素原子の原子比が
０．６０〜０．１５で表わされるポリアセン系骨格構造
を含有する不溶不融性基体と、（Ｂ）電子供与性ドーピ
ング剤又は電子受容性ドーピング剤とから成り、（Ｃ）
電気伝導性が未ドープの該基体よりも大であることを特
徴とする電気伝導性有機高分子系材料。が提案されてい
る。2. Description of the Related Art Polymer materials are excellent in moldability, lightness and mass productivity. Therefore, by utilizing these characteristics of the polymer material, an organic polymer material having electrical semiconductivity is demanded in many industrial fields including the electronics industry. The early organic semiconductors were difficult to mold into a film or plate, and did not have the properties of an n-type or p-type impurity semiconductor, so that their use was limited. In recent years, it has become possible to obtain organic semiconductors having relatively excellent moldability, and it is possible to obtain n-type or p-type organic semiconductors by doping these semiconductors with an electron-donating dopant or an electron-accepting dopant. It became. A typical example of such an organic semiconductor is polyacetylene. However, polyacetylene has a disadvantage that it is easily oxidized by oxygen. For this reason, it is difficult to handle in air, and it is not practical as an industrial material. Japanese Patent Application Laid-Open No. 59-3806, filed by the applicant of the present application, discloses a heat-treated product of (A) an aromatic polymer composed of carbon, hydrogen and oxygen, wherein the atomic ratio of hydrogen atoms / carbon atoms is 0. (C) comprising an insoluble and infusible substrate having a polyacene skeleton structure represented by the formula: (B) an electron-donating doping agent or an electron-accepting doping agent;
An electrically conductive organic polymer material having an electrical conductivity higher than that of the undoped substrate. Has been proposed.
【０００３】該材料は空気中で安定であり、工業材料と
して実用的である。しかしながら、この先願において
も、ポリアセン系骨格構造を有する不溶不融性基体から
なる有機高分子系材料を板状，円筒状等の成型体とする
時熱処理時の寸法安定性に問題があり、正確な寸法の材
料を得る事は難しく、また、大きなサイズの成型体を得
ようとした時、熱処理時にクラック等が発生するという
問題が残されていた。一方、セラミックス材料，炭素材
料等の様々な分野で粉末体を成型して目的とする形状の
製品を得る事は、一般的方法として知られており、成型
性に優れ、かつ高性能の粉末に対するニーズも大きい。
本願の出願人の出願に係る、特開平２−２１４７６２号
公報に記載の粉末材料では、結合剤と混合しただけで圧
縮成型すると、十分な強度を有する圧縮成型体を得るこ
とができなかった。[0003] The material is stable in air and is practical as an industrial material. However, this prior application also has a problem in dimensional stability at the time of heat treatment when an organic polymer material composed of an insoluble and infusible substrate having a polyacene skeleton structure is formed into a plate-like or cylindrical-like molded body. It is difficult to obtain a material having a large size, and when a large-sized molded body is to be obtained, there remains a problem that cracks and the like occur during heat treatment. On the other hand, it is known as a general method to obtain a product having a desired shape by molding a powder body in various fields such as ceramic materials and carbon materials. Needs are great.
With the powder material disclosed in Japanese Patent Application Laid-Open No. 2-214762, filed by the applicant of the present application, a compression molded body having sufficient strength could not be obtained by compression molding only by mixing with a binder.
【０００４】[0004]
【発明が解決しようとする課題】本発明者らは、ポリア
セン系骨格構造を含有する不溶不融性基体を粉砕し、粉
末化し、ＰＴＦＥ系結合剤を加え、混合・混練し、該混
練物を破砕して得られた顆粒状不溶不融性基体を圧縮成
型することにより上述の問題点を解決した。本発明の目
的は、半導性ないし導電体の電気伝導性を有し、且つ成
型性に優れた顆粒状粒子を圧縮成型することによって得
られる２次電池用電極を提供することにある。更に他の
目的および効果は以下の説明から明らかにされよう。DISCLOSURE OF THE INVENTION The present inventors pulverize and pulverize an insoluble and infusible substrate containing a polyacene-based skeleton structure, add a PTFE-based binder, mix and knead the mixture, and mix the kneaded material. The above-mentioned problems have been solved by compression-molding the granular insoluble and infusible substrate obtained by crushing. An object of the present invention is to provide an electrode for a secondary battery obtained by compression-molding granular particles having semiconductivity or electric conductivity of a conductor and excellent moldability. Still other objects and advantages will be apparent from the following description.
【０００５】[0005]
【課題を解決するための手段】本発明の上記目的は、炭
素・水素および酸素から成る芳香族系ポリマーの熱処理
物であって、水素原子／炭素原子の原子比が０．０５〜
０．５であるポリアセン系骨格構造を含有する不溶不融
性基体粉末に、ＰＴＦＥ系結合剤を加え、混合混練し、
該混練物を破砕して得られる顆粒状不溶不融性基体を圧
縮成型することを特徴とする２次電池用電極によって達
成される。An object of the present invention is to provide a heat-treated product of an aromatic polymer comprising carbon, hydrogen and oxygen, wherein the atomic ratio of hydrogen atoms / carbon atoms is from 0.05 to 0.05.
A PTFE-based binder is added to an insoluble and infusible base powder containing a polyacene-based skeleton structure of 0.5, mixed and kneaded,
This is achieved by an electrode for a secondary battery, wherein a granular insoluble and infusible substrate obtained by crushing the kneaded material is subjected to compression molding.
【０００６】上記のポリアセン系骨格構造を含有する不
溶不融性基体とは、特開昭５９−３８０６号公報に記載
される芳香族系縮合ポリマーを特定の条件で熱処理する
ことにより得られる。具体的には本発明に用いる該芳香
族系ポリマーは（ａ）フェノール・ホルムアルデヒド樹
脂の如き、フェノール性水酸基を有する芳香族系炭化水
素化合物とアルデヒド類の縮合物、（ｂ）キシレン変性
フェノール，ホルムアルデド樹脂（フェノールの一部を
キシレンで置換したもの）の如き、フェノール性水酸基
を有する芳香族系炭化水素化合物，フェノール性水酸基
を有さない芳香族系炭化水素化合物およびアルデヒドの
縮合物及び（ｃ）フラン樹脂が好適である。The insoluble and infusible substrate having the polyacene skeleton structure can be obtained by subjecting an aromatic condensation polymer described in JP-A-59-3806 to a heat treatment under specific conditions. Specifically, the aromatic polymer used in the present invention is (a) a condensate of an aldehyde with an aromatic hydrocarbon compound having a phenolic hydroxyl group such as a phenol-formaldehyde resin, (b) a xylene-modified phenol, formaldehyde A hydrocarbon resin having a phenolic hydroxyl group, an aromatic hydrocarbon compound having no phenolic hydroxyl group and a condensate of an aldehyde, such as a phenolic resin (having phenol partially substituted with xylene); ) Furan resins are preferred.
【０００７】本発明における不溶不融性基体は、上記の
如き芳香族系ポリマーの熱処理物であって例えば次のよ
うにして製造することができる。前記した芳香族系ポリ
マーに塩化亜鉛，リン酸ナトリウム等の無機塩を混合す
る。これにより、不溶不融性基体に多孔性を付与するこ
とができる。混入する量は、無機塩の種類及び目的とす
る電極の形状，性能によって異なるが、重量比で１０／
１〜１／７が好ましい。また、多孔性でありかつ連通孔
を有する基体を得る場合には、無機塩を芳香族系縮合ポ
リマーの２．５〜１０重量倍の量で用いることが好まし
い。このようにして得られた無機塩と芳香族系縮合ポリ
マーの混合物を、フィルム状，板状等の目的とする形と
なし、５０〜１８０℃の温度で２〜９０分間加熱するこ
とにより硬化成型する。かくして得られた硬化体を、次
いで非酸化性雰囲気中で４００〜８００℃の温度、好ま
しくは４５０〜７５０℃の温度、特に好ましくは５００
〜７００℃の温度まで加熱する。この熱処理によって芳
香族系縮合ポリマーは、脱水素脱水反応をおこし、芳香
環の縮合反応によって、ポリアセン系骨格構造が形成さ
れる。得られた熱処理体を水あるいは希塩酸等で十分洗
浄することによって、熱処理体中に含まれている無機塩
を除去する。その後、これを乾燥すると不溶不融性基体
が得られる。The insoluble and infusible substrate in the present invention is a heat-treated product of the aromatic polymer as described above, and can be produced, for example, as follows. An inorganic salt such as zinc chloride or sodium phosphate is mixed with the aromatic polymer. Thereby, porosity can be provided to the insoluble and infusible substrate. The mixing amount varies depending on the type of the inorganic salt and the shape and performance of the target electrode, but is 10/10 by weight.
1 to 1/7 is preferred. When a porous substrate having a communicating hole is to be obtained, the inorganic salt is preferably used in an amount of 2.5 to 10 times the weight of the aromatic condensation polymer. The mixture of the inorganic salt and the aromatic condensation polymer thus obtained is formed into a desired shape such as a film or a plate, and is heated and molded at a temperature of 50 to 180 ° C. for 2 to 90 minutes. I do. The cured product thus obtained is then placed in a non-oxidizing atmosphere at a temperature of 400 to 800 ° C., preferably at a temperature of 450 to 750 ° C., particularly preferably 500
Heat to a temperature of ７００700 ° C. By this heat treatment, the aromatic condensation polymer undergoes a dehydrogenation dehydration reaction, and a polyacene skeleton structure is formed by the condensation reaction of the aromatic ring. The obtained heat-treated body is sufficiently washed with water or diluted hydrochloric acid to remove the inorganic salt contained in the heat-treated body. Thereafter, this is dried to obtain an insoluble and infusible substrate.
【０００８】この反応は熱縮合重合の一種であり、反応
度は最終生成物の水素原子／炭素原子（以後Ｈ／Ｃと云
う）で表わされる原子数比によって表わされる。不溶不
融性基体のＨ／Ｃの値は０．０５〜０．５、好ましく
は、０．１５〜０．３５である。不溶不融性基体のＨ／
Ｃの値が０．５より大きい場合は、ポリアセン系骨格構
造が未発達なため電気伝導度が低く好ましくない。一
方、Ｈ／Ｃの値が０．０５より小さい場合、ドーピング
できるドーパント量が少なく好ましくない。次に該不溶
不融性基体を粉砕することによって、不溶不融性基体粉
末を得ることができる。本発明の不溶不融性基体粉末を
得るためには、当然のことながら装置の機種を選定する
ことが重要であるが、その中で一般に知られているボー
ルミル，振動ミル，ジェットミル等の微粉砕可能な装置
が好ましい。例えばボールミルによる粉砕の場合、粉砕
時間が数分〜１００時間が適当であるが、その時間は得
るものによって決定すべきものである。かくして該不溶
不融性基体粉末が得られる。さらに該粉末の平均粒径は
０．１〜５．０μｍ、好ましくは０．１〜２．０μｍで
ある。平均粒径が上限より大きい場合、該粉末を用いて
成型品とした時、実用的に十分な強度が得にくく、下限
より小さい場合、粉砕効率，粉砕時間の点から実用的で
ない。This reaction is a kind of thermal condensation polymerization, and the degree of the reaction is represented by the atomic number ratio represented by hydrogen atoms / carbon atoms (hereinafter referred to as H / C) in the final product. The H / C value of the insoluble infusible substrate is 0.05 to 0.5, preferably 0.15 to 0.35. H / of the insoluble infusible substrate
When the value of C is larger than 0.5, the electric conductivity is low because the polyacene skeleton structure is not developed, which is not preferable. On the other hand, if the value of H / C is smaller than 0.05, the amount of dopant that can be doped is small, which is not preferable. Next, the insoluble infusible substrate powder can be obtained by grinding the insoluble infusible substrate. In order to obtain the insoluble and infusible substrate powder of the present invention, it is naturally important to select the model of the apparatus. Pulverizable devices are preferred. For example, in the case of pulverization by a ball mill, a pulverization time of several minutes to 100 hours is appropriate, and the time should be determined depending on what is obtained. Thus, the insoluble and infusible substrate powder is obtained. Further, the average particle size of the powder is 0.1 to 5.0 μm, preferably 0.1 to 2.0 μm. If the average particle size is larger than the upper limit, it is difficult to obtain practically sufficient strength when the powder is used to form a molded product. If the average particle size is smaller than the lower limit, it is not practical in terms of pulverization efficiency and pulverization time.
【０００９】顆粒状不溶不融性基体は、上記不溶不融性
基体粉末にＰＴＦＥ系結合剤を加え、市販の混合機，ま
たは造粒機、例えばダルトン（株）製 品川ミキサー等
の混合機により混合する。このときのＰＴＦＥ系結合剤
としては、ポリテトラフルオロエチレン（ＰＴＦＥ），
ポリクロロトリフルオロエチレン（ＰＣＴＦＥ），テト
ラフルオロエチレン−エチレン共重合体（ＥＴＦＥ），
テトラフルオロエチレン−ヘキサフルオロプロピレン共
重合体（ＦＥＰ），テトラフルオロエチレン−パーフル
オロアルキルビニルエーテル共重合体（ＰＦＡ）等が挙
げられるがＰＴＦＥが特に好ましく、エマルジョンタイ
プでも粉末タイプでもよい。ＰＴＦＥ系結合剤量は、不
溶不融性基体粉末１００重量部に対し、３〜３０重量部
（固形分）が好ましい。得られた混合物を混練機により
混練する。混練機としては、二軸ローラー，ニーダー，
スクリュー押出機，らいかい機等があるが、練り作用の
行なえる装置であればなんでもよいが、二軸ローラーが
好ましい。次に得られた混練物を破砕し、顆粒状不溶不
融性基体を得る。破砕する装置は一般に知られているコ
ーヒーミル，カッティングミル等特に限定されるもので
はない。The granular insoluble infusible substrate is prepared by adding a PTFE-based binder to the insoluble infusible substrate powder and using a commercially available mixer or a granulator such as a Shinagawa mixer manufactured by Dalton Co., Ltd. Mix. At this time, as the PTFE-based binder, polytetrafluoroethylene (PTFE),
Polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE),
Examples thereof include a tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), but PTFE is particularly preferred, and an emulsion type or a powder type may be used. The amount of the PTFE-based binder is preferably 3 to 30 parts by weight (solid content) based on 100 parts by weight of the insoluble and infusible base powder. The obtained mixture is kneaded with a kneader. As the kneading machine, twin-screw roller, kneader,
Although there are a screw extruder and a grinder, any device capable of performing the kneading action may be used, but a biaxial roller is preferable. Next, the obtained kneaded material is crushed to obtain a granular insoluble and infusible substrate. The crushing device is not particularly limited, such as a commonly known coffee mill, cutting mill, and the like.
【００１０】さらにこの不溶不融性基体を乾燥し、圧縮
成型を行なう。該不溶不融性基体はそのままでも成型可
能であるが、その粒径を小さくして用いることもでき
る。粒径は１０〜２０００μｍが好ましいが、その粒径
は、成型物の形状により選択されるべきものである。成
型するための圧縮成型機は市販の打錠機を使用すること
により自動的に成型物となる。例えばロータリー型打錠
機あるいは単発式打錠機でよい。すなわち、臼部ときね
部とがあり、臼部に入った顆粒状粒子をかきとることに
より、一定量の粒子が臼部に入る。それを上下からきね
で圧縮し、抜き出すことにより、成型物、すなわち電池
用電極となる。かくして圧縮成型しやすい顆粒状粒子か
ら、２次電池用電極が得られる。[0010] Further, the insoluble and infusible substrate is dried and compression molded. The insoluble and infusible substrate can be molded as it is, but can also be used with its particle size reduced. The particle size is preferably from 10 to 2000 μm, but the particle size should be selected according to the shape of the molded product. A compression molding machine for molding is automatically formed into a molded product by using a commercially available tableting machine. For example, a rotary-type tableting machine or a single-shot tableting machine may be used. That is, there are a mortar and a tongue, and a certain amount of particles enter the mortar by scraping the granular particles that have entered the mortar. It is compressed and pulled out from above and below, forming a molded product, that is, a battery electrode. Thus, an electrode for a secondary battery is obtained from the granular particles that are easily compressed.
【００１１】[0011]
【発明の効果】本発明に係る２次電池用電極は、ポリア
セン系骨格構造を含有する不溶不融性基体粉末とＰＴＦ
Ｅ系結合剤との混合物を混練後、破砕することによって
得られる顆粒状不溶不融性基体を用いることにより圧縮
成型が可能で、充分な強度を有する電極となる。さらに
は臼部の形状を変えることにより、板状，円板状に成型
できる。以下、実施例により本発明を具体的に説明す
る。The electrode for a secondary battery according to the present invention comprises an insoluble infusible base powder containing a polyacene-based skeleton structure and PTF.
After kneading the mixture with the E-based binder and then crushing it, compression molding is possible by using a granular insoluble and infusible substrate, which results in an electrode having sufficient strength. Further, by changing the shape of the mortar portion, it can be formed into a plate shape or a disk shape. Hereinafter, the present invention will be described specifically with reference to examples.
【００１２】実施例 水溶性レゾール（約６０％濃度）／塩亜亜鉛／水を重量
比で１０／２５／４の割合で混合した水溶液を１００ｍ
ｍ×２ｍｍの型に流し込みその上にガラス板を被せ水分
が蒸発しない様にした後、約１００℃の温度で１時間加
熱して硬化させた。該フェノール樹脂をシリコニット電
気炉中に入れ窒素気流下で４０℃／時間の速度で昇温し
て、５００℃まで熱処理を行なった。次に該熱処理物を
希塩酸で洗った後、水洗いし、その後乾燥することによ
って板状の不溶不融性基体（Ｓ1 −１）を得た。上記
（Ｓ1 −１）の不溶不融性基体を、本願の出願人の出願
に係る、特開平２−２１４７６２号公報に記載のボール
ミルで平均粒径０．５μｍの不溶不融性基体粉末（Ｓ 1
−２）が得られるよう粉砕した。上記（Ｓ1 −２）の該
粉末１００部に対し、ＰＴＦＥ系結合剤１０部（固形
分）と水１５０部とを加え、ステンレスビーカーにて内
で混合した。 上記の混合物（Ｓ1 −３）を二軸ローラー
にて混練し、厚さ２ｍｍの板状の混練物（Ｓ1 −４）と
した。上記（Ｓ1 −４）の混練物をあらかじめ３〜５ｍ
ｍ角の大きさにカットし、さらにコーヒーミルにて破砕
し、顆粒状不溶不融性基体（Ｓ1 −５）とした。上記
（Ｓ1 −５）の顆粒状不溶不融性基体を圧縮成型機にて
厚さ１ｍｍ，直径１５ｍｍφの円板状に圧縮成型を行な
った。該成型物（Ｓ1 −６）の強度を確認するため、円
板状の該成型物を１０個抜き出し、直径部分から３０°
の角度に曲げてみたが、１０個中１０個とも割れは生じ
ていず、充分な強度を有していた。 比較例 実施例（Ｓ1 −２）と同様な方法で平均粒径０．５μｍ
の不溶不融性基体粉体（Ｓ0 −２）を作成した。該粉末
１００部に対し、ＰＴＦＥ３０部（固形分）と、水１５
０部とを加え、ステンレスビーカー内で混合した。 上記
の混合物（Ｓ 0 −３）を、混練する事無く且つ破砕する
事無く、へらで攪拌し、乾燥し、顆粒状不溶不融性基体
（Ｓ0 −５）を得た。 該基体（Ｓ0 −５）を実施例と同
様な方法で圧縮成型を行ない、該成型物の強度を１０個
試験したが、１０個中１０個とも３０°の角度に曲げる
とわれてしまった。EXAMPLE A water-soluble resol (about 60% concentration) / zinc chloride / water was added by weight.
100m of the aqueous solution mixed at a ratio of 10/25/4
Pour into a m × 2mm mold and cover with a glass plate.
After heating to a temperature of about 100 ° C for 1 hour.
Heated and cured. The phenolic resin was
Put in a furnace and heat at a rate of 40 ° C./hour under a nitrogen stream.
Then, heat treatment was performed up to 500 ° C. Next, the heat-treated product
After washing with dilute hydrochloric acid, wash with water and then dry.
Is a plate-like insoluble infusible substrate (S1-1) was obtained. the above
(S1-1) The insoluble infusible substrate was applied to the applicant's application
And the ball described in JP-A-2-214762
Insoluble and infusible substrate powder with an average particle size of 0.5 μm in a mill(S 1
-2)Was crushed to obtain. The above (S1-2)
For 100 parts of powder, 10 parts of PTFE-based binder (solid
Minutes) and 150 parts of water, and put in a stainless beaker.
And mixed. The above mixture (S1-3) is a biaxial roller
And a 2 mm-thick plate-shaped kneaded product (S1-4) and
did. The above (S1-4) 3 to 5 m beforehand
Cut to the size of m square, then crushed in a coffee mill
And a granular insoluble and infusible substrate (S1-5). the above
(S1-5) The granular insoluble and infusible substrate is compressed with a compression molding machine.
Compression molding into a disk with a thickness of 1mm and a diameter of 15mmφ
Was. The molded product (S1To check the strength of -6), use a circle
10 plate-shaped moldings were extracted and 30 ° from the diameter
I bent it at an angle of 10 but cracks occurred in 10 out of 10
And had sufficient strength. Comparative example Example (S1The average particle size is 0.5 μm in the same manner as in -2).
Insoluble infusible substrate powder (S0-2) was prepared. The powder
For 100 parts, 30 parts of PTFE (solid content) and 15 parts of water
0 copiesAnd addIn a stainless beakerMixed. the above
Mixture (S 0 -3) is crushed without kneading
Without any problems, stir with a spatula,Dry and granular insoluble infusible substrate
(S0-5) was obtained. The substrate (S0-5) as in Example
Perform compression molding by the same method and reduce the strength of the molded product to 10
Tested, but 10 out of 10 bends at an angle of 30 °
I was told.
フロントページの続き (56)参考文献 特開 平３−147261（ＪＰ，Ａ) 特開 昭61−80774（ＪＰ，Ａ) 特開 昭59−3806（ＪＰ，Ａ) 特開 平２−214762（ＪＰ，Ａ) 特開 平６−60864（ＪＰ，Ａ) 特開 平６−60866（ＪＰ，Ａ)Continuation of the front page (56) References JP-A-3-147261 (JP, A) JP-A-61-80774 (JP, A) JP-A-59-3806 (JP, A) JP-A-2-214762 (JP) JP-A-6-60864 (JP, A) JP-A-6-60866 (JP, A)
Claims (1)
合ポリマーの熱処理物であって、水素原子／炭素原子の
原子比が０．０５〜０．５であるポリアセン系骨格構造
を含有する不溶不融性基体粉末に、ポリテトラフルオロ
エチレン系結合剤を加え、混合・混練し、該混練物を破
砕して得られる顆粒状不溶不融性基体を圧縮成形するこ
とを特徴とする２次電池用電極。1. A heat-treated product of an aromatic condensed polymer comprising carbon / hydrogen and oxygen, wherein said heat-treated insoluble material has a polyacene skeleton structure having an atomic ratio of hydrogen atom / carbon atom of 0.05 to 0.5. A secondary battery characterized in that a polytetrafluoroethylene-based binder is added to an infusible substrate powder, mixed and kneaded, and a granular insoluble infusible substrate obtained by crushing the kneaded material is compression-molded. Electrodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4233147A JP2723763B2 (en) | 1992-08-06 | 1992-08-06 | Electrodes for secondary batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4233147A JP2723763B2 (en) | 1992-08-06 | 1992-08-06 | Electrodes for secondary batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0660865A JPH0660865A (en) | 1994-03-04 |
| JP2723763B2 true JP2723763B2 (en) | 1998-03-09 |
Family
ID=16950461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4233147A Expired - Lifetime JP2723763B2 (en) | 1992-08-06 | 1992-08-06 | Electrodes for secondary batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2723763B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3253859B2 (en) * | 1996-08-09 | 2002-02-04 | 東芝電池株式会社 | Non-aqueous solvent secondary battery and method for granulating negative electrode mixture thereof |
-
1992
- 1992-08-06 JP JP4233147A patent/JP2723763B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0660865A (en) | 1994-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Dispersion of graphite nanosheets in a polymer matrix and the conducting property of the nanocomposites | |
| JP3002114B2 (en) | Manufacturing method of battery electrode | |
| JP3438865B2 (en) | Fuel cell separator, method for producing the same, and fuel cell using the separator | |
| Titelman et al. | Thermal dynamic processing of polyaniline with dodecylbenzene sulfonic acid | |
| JP2723763B2 (en) | Electrodes for secondary batteries | |
| CN108341929A (en) | A kind of Graphene epoxy resin composite material and preparation method thereof | |
| JP2000173630A (en) | Method for manufacturing separator member for polymer electrolyte fuel cell | |
| JP3455466B2 (en) | Fuel cell and fuel cell separator | |
| JP2702854B2 (en) | Electrodes for secondary batteries | |
| Yang et al. | Polypyrrole—polypropylene composite films: preparation and properties | |
| JP2843261B2 (en) | Manufacturing method of battery electrode mixture | |
| JP2702853B2 (en) | Electrodes for secondary batteries | |
| Roichman et al. | Percolation of electrical conductivity in solution-cast blends containing polyaniline | |
| JP2002216788A (en) | Manufacturing method of carbonaceous molded products | |
| JP2837427B2 (en) | Electrically conductive organic polymer materials | |
| CN1280348C (en) | Metal-doped low-density poly-4-methyl-1-pentene foam material and preparation method thereof | |
| JPH08311173A (en) | Production of insoluble and infusible base having polyacene-based skeleton structure | |
| JP2003257447A (en) | Separator for fuel cell, manufacturing method therefor, and fuel cell by use of separator for fuel cell | |
| JP2521110B2 (en) | Method for producing conductive resin composition | |
| JP2632421B2 (en) | Battery electrode | |
| JP2002155149A (en) | Manufacturing method of carbonaceous powder molding material | |
| JP2601777B2 (en) | Electrodes for organic electrolyte batteries | |
| JPH02214762A (en) | Electroconductive organic polymer-based power material and production thereof | |
| JP2023127697A (en) | Conductive polymer capsule and liquid mixture therewith, as well as manufacturing method of carbon fiber composite material | |
| JP2668229B2 (en) | Organic semiconductor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S202 | Request for registration of non-exclusive licence |
Free format text: JAPANESE INTERMEDIATE CODE: R315201 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121128 Year of fee payment: 15 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121128 Year of fee payment: 15 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121128 Year of fee payment: 15 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121128 Year of fee payment: 15 |